Ultrafast Carrier Dynamics in CdSe/CdS/ZnS Quantum Dots

The intra- and inter-band relaxation dynamics of CdSe/CdS/ZnS core/shell/shell quantum dots are investigated with the aid of time-resolved nonlinear transmission spectra which are obtained using femtosecond pump-probe technique. By selectively exciting the core and shell carrier, the dynamics are studied in detail. Carrier relaxation is found faster in the conduction band of the CdS shell （about 130 fs） than that in the conduction band of the CdSe core （about 400 fs）. From the experiments it is distinctly demonstrated the existence of the defect states in the interface between the CdSe core and the CdS shell, indicating that ultrafast spectroscopy might be a suitable tool in studying interface and surface morphology properties in nanosystems.

氢氟酸处理InP/GaP/ZnS量子点的光学性能及其发光二极管应用

采用氢氟酸(HF)原位注入法制备了InP/GaP/ZnS量子点。通过紫外/可见/近红外光谱、光致发光光谱、透射电镜、球差校正透射电镜、X射线衍射、X射线光电子能谱等测试手段分析了HF对InP量子点的发光性能影响。实验结果表明,HF刻蚀减少了量子点表面氧化缺陷状态,有效控制了InP核表面的氧化,并且原子配体形式的F-钝化了量子点表面的悬挂键,显著提升了量子点的光学性能。HF处理的InP/GaP/ZnS量子点具有最佳的发光性能,PLQY高达96%。此外,用HF处理InP/GaP/ZnS量子点制备的发光二极管,其发光的电流效率为6.63 cd/A,最佳外量子效率(EQE)为3.83%。

Synthesis and characterization of ZnS-based quantum dots to trace low concentration of ammonia

In the present work,a solution-based co-precipitation method has been adopted to synthesize pure and cobalt-doped ZnS quantum dots and characterized by XRD,SEM,TEM with EDX,FTIR and gas sensing properties.XRD analysis has shown a single phase of ZnS quantum dots having a zinc blend structure.TEM and XRD line broadening indicated that the average crystallite size in the sample is in the range of 2 to 5 nm.SEM micrographs show spherical-shaped quantum dots.FTIR studies show that cobalt has been successfully doped into the ZnS cubic lattice.EDX spectra have analyzed the elemental presence in the samples and it is evident that the spectra confirmed the presence of cobalt(Co),zinc(Zn),oxygen(O),and sulphur(S)elements only and no other impurities are observed.The ZnS-based quantum dot sensors reveal high sensitivity towards 50 ppm of ammonia vapors at an operating temperature of 70℃.Hence,ZnS-based quantum dots can be a promising and quick traceable sensor towards ammonia sensing applications with good response and recovery time.

Large-scale control of enhancement and quenching of photoluminescence for ZnSe/ZnS quantum dots and Ag nanoparticles in aqueous solution

We investigated the optical properties of hybrid exciton–plasmon coupling ensembles composed of ZnSe/ZnS quantum dots and Ag nanoparticles in aqueous solution. We modulated their average interval by changing the ratio of quantum dots and Ag nanoparticles. The transition from dramatic PL enhancement to PL quenching state was experimentally observed, according to the continuous decrease of the PL lifetime. The PL enhancement rate exceeded 10, with the Purcell factor of 3.5. Meanwhile, the proportion of fast decay increased from 0.3 to 0.6, corresponding to the proportion of slow decay decreased from 0.7 to 0.4. Our experiment is important for the hybrid exciton–plasmon coupling system to be practicable in optoelectronic application.

Temperature dependence of the photoluminescence of MnS/ZnS core–shell quantum dots

The temperature dependence of the photoluminescence（PL） from Mn S/Zn S core–shell quantum dots is investigated in a temperature range of 8 K–300 K. The orange emission from the ^4T1→^6A1transition of Mn^2＋ions and the blue emission related to the trapped surface state are observed in the Mn S/Zn S core–shell quantum dots. As the temperature increases, the orange emission is shifted toward a shorter wavelength while the blue emission is shifted towards the longer wavelength. Both the orange and blue emissions reduce their intensities with the increase of temperature but the blue emission is quenched faster. The temperature-dependent luminescence intensities of the two emissions are well explained by the thermal quenching theory.

Water-soluble CdSe/ZnS quantum dots passivated by poly(glycino amino acid) phosphazenes

Poly(organophosphazenes) have potential applications in making water-soluble and biocompatible quantum dots (QDs) due to their wide variety of properties. The CdSe QDs of green emission and the core-shell CdSe/ZnS QDs of red emission were prepared. Subsequently the trioctylphosphine oxide-stabilized CdSe/ZnS QDs were transferred from chloroform into water through a ligand exchange process with poly(glycino amino acid)phosphazenes, which can be obtained from the saponification of poly (glycino amino ester)phosphazenes at room temperature. The resulting QDs-polymer nanocomposite particles can form colloidally stable suspensions in water and exhibit good photostability.

In-situ Synthesis of SnO2 Quantum Dots/ZnS Nanosheets Heterojunction as a Visible-light-driven Photocatalyst for Degradation of Rhodamine B,Potassium Dichromate and Tetracycline

The SnO2 quantum dots(SnO2QDs)/ZnS nanosheets(ZnSNs)heterojunction was fabricated via an in-situ synthetic method at room temperature.Rhodamine B,potassium dichromate,and tetracycline were used to discuss the photocatalytic activities of the as-prepared samples under the visible light illumination.The photocatalytic mechanism of the as-prepared samples was also proposed.The experimental results indicate that the degradation efficiency of the as-prepared SnO2QDs/ZnSNs heterojunction first increases and then decreases with increasing the usage of ZnSNs.When the mass ratio of SnO2QDs to ZnSNs is 1:2 in 180 min,the as-prepared samples have the highest degradation efficiency of 89.1%for rhodamine B,97.7%for potassium dichromate,and 83.8%for tetracycline,which are much higher than 51.7%,26.8%,and 0.9%of pure SnO2QDs as well as 37.9%,87.1%,and 19.1%of pure ZnSNs,respectively.After it is repeatedly degraded for 3 times,it possesses the degradation efficiency of 62.5%for rhodamine B,which increases by 200.5%in comparison with 20.8%of the pure SnO2QDs.Moreover,the enhanced photocatalytic performances of the as-prepared hybrids are attributed to the formation of heterojunction between the SnO2QDs and ZnSNs.In addition,hydroxyl radicals and superoxide anion radicals play major roles during the photocatalytic degradation process,while holes play a minor role.

Effect of gamma irradiation on optical properties of CdSe/ZnS quantum dots embedded in PDMS

The optical properties of CdSe/ZnS quantum dots(QDs)embedded in polydimethylsiloxane(PDMS)flexible materials after irradiated withγ-rays were studied.As an embedding matrix,PDMS exhibits the advantage of high radiation hardness.The luminescence spectra and fluorescence lifetime of the irradiated and unirradiated samples were tested.The fluorescence intensity of QDs decreases with the increase of the irradiation dose according to the result of luminescence spectra.The fluorescence intensity of the QDs decreases by 80%after irradiation with a dose of 1 kGy,but the position of the emission peak and the spectral shape of the QDs remain consistent before and after irradiation.In addition,the fluorescence lifetime of QDs is shortened after irradiation.Based on the fluorescence response of QDs to the irradiation ofγ-rays and combined with flexible materials,our work provides a theoretical basis for the application of QDs as a new wearable dosimeter.

组分对Cu-Zn-In-S/ZnS核壳量子点发光性能的影响

利用热注射法通过调控Cu/Zn比例制备了不同组分的Cu-Zn-In-S/ZnS核壳量子点,通过紫外-可见吸收光谱以及稳态和时间分辨光谱分析Cu/Zn比例对量子点发光性能的影响.结果表明,不同组分Cu-Zn-In-S/ZnS核壳量子点呈现闪锌矿结构且晶粒尺寸接近;随着Cu/Zn比例的减小,Cu-Zn-In-S/ZnS核壳量子点的带隙变宽,导致吸收光谱发生蓝移;当Cu/Zn比例从6/1减小到1/6时,量子点的发光峰位从640nm蓝移529nm.由于Zn2+替代Cu+能够减少Cu原子缺陷的形成,从而提高了量子点的荧光效率;当Cu/Zn=1/6时,样品中观测到Cu+离子发光和较长的荧光寿命.

ZnCuInS/ZnSe/ZnS量子点发光光谱特性的研究

ZnCuInS/ZnSe/ZnS量子点是一种无毒,无重金属的'绿色'半导体纳米材料。在研究中,制备了三种尺寸的ZnCuInS/ZnSe/ZnS核壳量子点,其直径分别为3.3,2.7,2.3nm。通过测量不同尺寸的ZnCuInS/ZnSe/ZnS量子点的光致发光光谱,其发射峰值波长随尺寸的减小而蓝移。其吸收峰值波长和发射峰值波长分别是510,611(3.3nm),483,583(2.7nm)以及447,545nm(2.3nm)。ZnCuInS/ZnSe/ZnS量子点具有显著的尺寸依赖效应。ZnCuInS/ZnSe/ZnS量子点的斯托克斯位移分别为398meV(3.3nm),436meV(2.7nm)以及498meV(2.3nm),这样大的斯托克斯位移证明,ZnCuInS/ZnSe/ZnS量子点的发光机制与缺陷能级有关。同时,对直径为3.3nm的ZnCuInS/ZnSe/ZnS量子点进行了温度依赖的光致发光光谱的测量,当温度为15～90℃时,该量子点发射峰值波长随温度的升高而红移,发光强度随温度的升高而降低,说明ZnCuInS/ZnSe/ZnS量子点是以导带能级与缺陷能级之间跃迁为主的复合发光。

ZnSe:Cu/CdS核壳量子点的合成及光学性能研究

以CdS为壳层材料对核水溶性ZnSe:Cu量子点进行包覆,得到ZnSe:Cu/CdS核壳结构的量子点。研究了壳层厚度对ZnSe:Cu量子点光学性能的影响,采用TEM、XRD、PL和UV-Vis手段对所得样品进行表征。实验结果表明:量子点为立方闪锌矿结构,分散性好,形状为球形,经壳层修饰后量子点的粒径由2.7 nm增大到4.0 nm。随着包覆CdS壳层数的增加,量子点的发射和紫外吸收谱红移,说明量子点在长大,证明CdS壳层生长在ZnSe:Cu量子点的表面,形成了核壳结构的ZnSe:Cu/CdS量子点。包覆CdS壳层后ZnSe:Cu量子点的发光强度减弱,但稳定性得到了提高。

ZnCuInS/ZnS量子点与Poly-TPD补偿发光光谱的研究

ZnCuInS/ZnS量子点是一种无重金属、'绿色'半导体纳米材料。在研究中,制备出尺寸为3.2nm的ZnCuInS/ZnS核壳量子点,并说明它是施主-受主对复合发光。通过测量ZnCuInS/ZnS量子点的光致发光光谱,其发射峰值波长为620nm、半宽度是95nm的红光。同时,还制备出Poly-TPD有机薄膜,其发光光谱是峰值波长为480nm的蓝光。所以,ZnCuInS/ZnS量子点和Poly-TPD发光颜色具有互补性。在Zn-CuInS/ZnS量子点薄膜层上包覆一层poly-TPD薄膜后,二者发光颜色互补。在恰当的偏置电压下,可以得到较好的白光光谱。计算表明,其色坐标是(0.336,0.339),颜色指数是92。

基于Mn∶ZnS量子点-Cu^(2+)体系室温磷光猝灭-恢复方法测定水体中焦磷酸根离子

以谷胱甘肽(GSH)为稳定剂,成功合成了高性能的水溶性Mn∶ZnS量子点(Quantum dots,QDs).Mn∶ZnS QDs表面的羧基能与Cu^(2+)结合从而有效引发QDs电子转移,致使Mn∶ZnS QDs室温磷光显著猝灭.当体系中加入焦磷酸(PPi)时,由于Cu^(2+)与PPi的结合能力强于Mn∶ZnS QDs表面的羧基,Mn∶ZnS QDs磷光强度又逐渐恢复.据此建立一种基于Mn∶ZnS QDs-Cu^(2+)体系的室温磷光探针测定焦磷酸根离子的新方法.该方法灵敏、简单,线性范围为5.0×10^(-8)—1.0×10^(-4)mol·L^(-1),检测限为1.0×10^(-8)mol·L^(-1).经过干扰实验及添加回收率实验证实,该方法具有良好的选择性,满足于实际样品水体中焦磷酸的检测分析.

ZnCuInS/ZnS量子点荧光粉LED发光特性研究

ZnCuInS/ZnS(QDs)量子点是一种不含重金属半导体的纳米材料,以无机前驱体和非配位溶剂为基础,合成得到尺寸为3.2nm的ZnCuInS/ZnS核壳量子点,通过测量ZnCuInS/ZnS量子点光致发光光谱,其发射峰波长约为700nm,半宽度为110nm。同时,以GaN蓝光芯片为基础,制备了ZnCuInS/ZnS量子点荧光粉LED发光二极管,并对其发光特性进行了研究。在恰当的偏置电压下,逐渐改变滴涂在底层为蓝色GaN LED芯片上的ZnCuInS/ZnS量子点溶液浓度,观察到红光逐渐增强,随之蓝光逐渐减弱,其发射光CIE色坐标发生改变,并可以得到较好的红光光谱。

核壳型ZnS∶Cu/ZnS量子点的制备及发光性质

本文采用水相合成方法制备了ZnS∶Cu量子点并进行了ZnS壳层修饰,研究了壳层厚度对ZnS∶Cu量子点光学性质的影响,采用TEM、XRD、PL、PLE和UV-Vis等测试方法对其进行了表征。实验结果表明,合成的ZnS∶Cu/ZnS量子点为立方闪锌矿,尺寸分布均匀呈球形,分散性良好,经过壳层修饰平均粒径由2 nm增加到3.2 nm。随着ZnS壳与ZnS核量的比的增加,量子点的PLE激发峰位置和UV-Vis吸收谱线出现红移,也说明了量子点的尺寸增大,证明ZnS在ZnS∶Cu量子点的表面生长,形成了核壳结构的ZnS∶Cu/ZnS量子点。随着壳层增厚,量子点与铜离子发光中心相关的发射峰强度先增大后减小,当壳核比ns/nc=2.5时,发光强度达到最大。

MRI增强CIS/ZnS/GdS量子点对水溶液中Cu^(2+)的选择性检测

铜是人体必需的微量元素,但过量的铜的摄入会扰乱细胞的内稳态,引起不同类型的神经退行性疾病.近年来,随着工业的发展,大量的铜通过各种途径泄漏到环境中,成为大量的饮用水污染物.因此,开发高灵敏度、高选择性的铜离子探测探针是十分必要和具有挑战性的.本文采用成本低、操作简单的MRI增强量子点-CuInS2/ZnS/GdS材料作为选择性铜(Cu^(2+))离子探针,对离子进行高灵敏度、高选择性的检测.当加入不同浓度的Cu^(2+)时,CuInS2/ZnS/GdS量子点的荧光强度降低,而加入其他金属离子(如Al^(3+)、Sn^(2+)、Zn^(2+)、Fe^(2+)、Mn^(2+)、Ca^(2+)、Na+和Gd^(3+))时,量子点的荧光强度不变.计算得到的Cu^(2+)检出限可低至0.5ppb.该方法的感应机制可能是Cu^(2+)诱导CuInS2/ZnS/GdS量子点聚集和沉淀而导致的荧光猝灭.

硫脲修饰ZnSe:Cu量子点的水相合成及荧光特性

以3-巯基丙酸为稳定剂在水相中合成了Cu掺杂的ZnSe量子点(QDs),并利用硫脲(CH4N2S)对其进行表面修饰,制备出核壳结构的ZnSe:Cu/ZnS量子点.制得的量子点呈闪锌矿结构,尺寸约为5nm,有较好的分散性。其荧光发射峰在460nm左右.经CH4N2S修饰后,量子点表面形成了宽禁带的ZnS包覆层,将电子和空穴限域在了ZnSe:Cu核内,减少了表面发生非辐射复合的载流子,显著提高了量子点的荧光强度.与Na2S、硫代乙酰胺(TAA)等常用硫源相比,以CH4N2S为硫源制得的ZnSe:Cu/ZnS量子点壳层厚度可控,表面钝化效果更好,显示出更佳的荧光效率和稳定性.ZnSe:Cu/ZnS量子点经过紫外线照射后消除了表面的悬空键,进一步提高了其量子产率,最终获到了具有较好荧光性质的ZnSe:Cu/ZnS量子点.

基于CuInS_2/ZnS核壳结构量子点的高光效暖白光LED

采用逐步热注射法合成了用于白光LED的Cu In S2/Zn S(CIS/Zn S)核壳结构量子点。通过调整Cu/In的比率,在Cu In S2(CIS)量子点的基础上,合成了发射波长在570~650 nm之间可调的CIS/Zn S量子点。与CIS量子点的低量子产率相比,具有核壳结构的CIS/Zn S量子点的量子产率达到了78%。通过在黄光荧光粉YAG∶Ce3+表面旋涂CIS/Zn S量子点的方式制备了暖白光LED器件。在工作电流为10 m A时,暖白光LED的发光效率达到了244.58 lm/W。由于CIS/Zn S量子点的加入,所制备的白光LED器件的显色指数达到86.7且发光颜色向暖色调发生了转移,相应的色坐标为(0.340 6,0.369 0)。

离子液体辅助微波法水相合成Cu-In-Zn-S/ZnS量子点及其在白光LED中的应用

Cu-In-Zn-S(CIZS)量子点具有毒性低、发射谱覆盖范围广、Stokes位移大等特点,在照明领域具有广阔的应用前景。通过离子液体辅助微波法水相合成CIZS量子点,系统研究了反应时间、配体添加量和前驱体溶液pH对样品的物相组成、显微形貌以及荧光性能的影响。结果表明,与未添加离子液体制备的样品相比,离子液体的引入提高了反应速率,可有效地将反应时间由180min缩短至30min;随着反应时间的延长,量子点的粒径增大,其发射峰位由609.2nm红移至634.6nm。随着nGSH(谷胱甘肽)/n(CuInZn)的增大,量子点的粒径逐渐增大,导致其发射峰位由622.6 nm红移至631.6 nm,同时量子点的发光强度逐渐增强;当该比值为15时,量子点的荧光强度最高。此外,随着pH的增大,去质子化的–SH和–NH2与量子点的作用逐渐增强,有效地钝化了量子点的表面态,使其荧光强度逐渐上升,当pH为8.5时,样品的荧光性能最佳,同时量子点的平均水合粒径由99nm增大至241nm;量子点溶液的Zeta电位为–27.7~–41.1mV,说明量子点溶液具有优异的稳定性。通过ZnS表面修饰可有效提高量子点的荧光强度。将CIZS/ZnS量子点与蓝光芯片结合,获得了显色指数为85.6、发光效率为34.8 lm/W的白光LED器件,为水相制备的多元量子点在白光LED中的应用提供了参考。

掺杂Cu^(2+)的ZnS量子点的制备和光学性能研究

量子点由于特殊的结构特点,显示出良好的光电性能,受到广泛的应用。然而其具有的生物毒性违背了环境友好型可持续发展战略,日益受到人们的关注。ZnS作为一种低毒低污染的半导体材料,是目前的研究热点。但单纯的ZnS量子点带隙较宽,电子跃迁所需吸收的光子较多,故难以产生稳定且性能良好的发光。通过掺杂Cu^(2+)后,ZnS量子点的发光效率提高,光电性能更为稳定,且保持低毒低污染的优势。文章中采用热注入法制备出ZnS量子点并掺杂Cu^(2+),通过X射线衍射图谱(XRD)、透射电子显微镜(TEM)以及荧光光谱(PL)对上述样品进行表征。ZnS量子点呈颗粒状均匀分布,具有六方纤锌矿结构;其发光强度较弱,在约470 nm和540 nm左右显示发光峰,分别对应本征峰和表面缺陷峰。掺杂Cu^(2+)后量子点的发光性能得到了显著地提高。此外进一步研究了S含量、Cu^(2+)掺杂量和加入硫源((NH4)2S)后的反应时间对ZnS:Cu量子点发光性能的影响。